JPH05503116A - Method for producing multilayer lacquer coatings and aqueous basecoat lacquers suitable for this method - Google Patents

Abstract

PCT No. PCT/EP91/00448 Sec. 371 Date Nov. 30, 1992 Sec. 102(e) Date Nov. 30, 1992 PCT Filed Mar. 9, 1991 PCT Pub. No. WO91/14515 PCT Pub. Date Oct. 3, 1991.The invention relates to basecoats for the production of finishes of the basecoat/clearcoat type which comprise a water-thinnable polyacrylate resin which can be obtained by polymerizing, either successively or in part amounts, monomers containing carboxyl groups and monomers free from carboxyl groups in an organic solvent to form a polyacrylate resin which is neutralized, at least partially, and dispersed in water.

Description

[Detailed description of the invention] 8 Component (β) is 50 to 80 mol% aromatic polycarboxylic acid and/or cyclic polycarboxylic acid, and 20 to 50 mol% of one or more polycarboxylic acids. Consisting of molecular weight fatty acids, in this case high molecular weight fatty acids are cycloaliphatic polycarboxylic acids. The method or lacquer according to claim 7, which is not considered.

9. Undercoat/clear coat type multilayer coating, protective coating and/or decorative coating According to any one of claims 2 to 8 as a base lacquer for the manufacture of Use of water-based lacquers as described.

For the production of base multilayer lacquer coatings containing exclusively organic solvents as solvents and/or solvents. method and a water-based basecoat lacquer suitable for this method. The present invention relates to a method for producing multilayer coatings, protective coatings and/or decorative coatings. In this case, (1) an aqueous base coat containing pigment as the base lacquer; A varnisher is applied onto the support surface; (2) A thin polymer film is formed from the lacquer applied in step (1); (3) A transparent top lacquer is applied on the base layer thus obtained, and then (4) This method, in which the base layer is baked together with the top lacquer, is a well-known Primer/clear coat method, and above all, this method is gaining value in the automotive industry. Used for the production of high-quality top lacquer coatings, especially metallic lacquer coatings (e.g. For example, European Patent Application No. 38127, European Patent Application No. 89497 and (see Federal Republic of Italy Patent Application No. 3,628,124).

The present invention also provides a water-based lacquer that can be used as a base lacquer by the above method. Also related.

In the case of the primer/clear coat method described, 1 coat of diluted 7 coats will be used as raw material. used.

Ranker Industries, for ecological and economic reasons, uses organic solvents as much as possible. Efforts are being made to replace some parts with water. Used in the basecoat/clearcoat method above. There is a great need for water-based basecoat lacquers that can be used. Undercoat/clear coat method book The qualitative feature is that a transparent top lacquer is applied onto an unbaked base layer. The base layer and top lacquer are then baked together. (overcoat, Na5s-4n-Nass-Verfahren).

The challenge of the present invention is that it can be used as a base lacquer in the basecoat/clearcoat process. The objective is to provide a novel water-based lacquer. This challenge, surprisingly, contains pigments The solution is to provide a water-based lacquer with a (r) (al) having at least one carboxyl group per molecule, (bl), ( b2), an ethylenically unsaturated monomer copolymerizable with (b3) and (a2), or The mixture of such monomers contains 2.5 to 15% by weight, preferably 3 to 7% by weight. Beauty (a2) does not have a carboxyl group, (bl), (b2), (b3) and (a l) copolymerizable with ethylenically unsaturated monomers or mixtures consisting of such monomers; 0 to 60% by weight, preferably 0 to 28% by weight of the compound and (b1) can be copolymerized with (b2), (b3), (al) and (a2), (meth)acrylic acid esters essentially free of carboxyl groups or such from 40 to 90% by weight, preferably from 40 to 90% by weight, of (meth)acrylic acid esters. 80% by weight and copolymerized with (b2) (bl), (b3), (al) and (a2) have at least one hydroxyl group per molecule and are essentially carbonaceous. Ethylenically unsaturated monomers that do not have carboxyl groups or such monomers from 0 to 45% by weight, preferably from 4 to 34% by weight, and (b3) copolymerizable with (bl), (b2), (al) and (a2), essentially Ethylene-based, different from (bl) and (b2), which does not have a carboxyl group in 0 to 40% by weight of unsaturated monomers or mixtures of such monomers, preferably 1 Component (b) consisting of 0 to 30% by weight is added sequentially or alternately in portions to an organic solvent or or a solvent mixture and polymerized in the presence of at least one polymerization initiator, (II) After termination of the polymerization, the obtained polyacrylate resin is at least partially neutralized and dispersed in water, in this case (al), (a2), (bl), (b2 ) and (b3), the sum of the weight needles is always 100% by weight, and (bl), (b2), (b3), (al) and (a2) are boria in terms of type and amount. 'The acrylate resin has a hydroxyl value of 0 to 200, especially 20 to 120, 20 to an acid number of 100, especially 25 to 50 and -40°C to +60°C, especially -20°C to +4 obtained by selecting a glass transition temperature (Tc) of 0°C. It is characterized by containing a water-dilutable polyacrylate resin.

The water-dilutable polyacrylate resin used according to the invention is particularly suitable for the known polyacrylate resins. Increased solids content and low spreading compared to acrylate resin-containing base lacquers It makes it possible to prepare base lacquers that have a tendency to elongate. Furthermore, the present invention The use of water-dilutable polyacrylate resins by In the case of lacquers, this results in stabilization against varying shear loads. In particular, weak shear In the case of force loading, less viscosity reduction may occur compared to the state of the art. Otherwise, no viscosity reduction occurs. This results in improved settling behavior, easier handling and results in increased application safety.

The production of essential water-dilutable polyacrylate resins is described in detail in the present invention. Before that, an explanation of two concepts will be given first. 1) “Methacrylic acid or acrylic acid” may be omitted in some cases. (meth)acrylic acid is used.

2.) The expression “essentially free of carboxyl groups” refers to components (bl), ( b2) and (b3) have a small carboxyl group content (but at most (bl), (b2) and (b3)) It represents that. However, the components (bl), (b2) and (b3) The boxyl group content is advantageously kept as low as possible. Particularly advantageously, (bl), (b2) and (b3) components completely free of carboxyl groups are used be done.

For the production of the polyacrylate resin to be used according to the invention, the component (al) As, (a2), (with one carboxyl group per molecule) All ethylenically unsaturated monomers copolymerizable with bl), (b2) and (b3) Alternatively, mixtures of such monomers may be used. Ingredient (al) In particular, acrylic acid and/or methacrylic acid are used. However, in the molecule Other ethylenically unsaturated acids having up to 6 carbon atoms may also be used.

Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, and fumaric acid. and itaconic acid. As the component (al), for example, succinic acid mono(meth) ) Acryloyloxyethyl ester and heptano(meth)acryloyl phthalate Oxyethyl esters may also be used.

As component (a2), it can be copolymerized with (bl), (b2), (b3) and (al). All capable ethylenically unsaturated monomers or mixtures of such monomers may be used. may be used. As component (a2), components (bl), (b2) and (b3) All monomers mentioned when describing may be used.

As component (bl), it can be copolymerized with (b2), (b3), (al) and (a2). All (meth)acrylic acid esters or esters with essentially no carboxyl group. or mixtures consisting of such (meth)acrylic esters may be used. . Examples include alkyl acrylates with up to 20 carbon atoms in the alkyl group. salts and alkyl methacrylates, such as methyl acrylate, ethyl acrylate rate, propyl acrylate, butyl acrylate, hexyl acrylate, Ethylhexyl acrylate, stearyl acrylate and lauryl acrylate methyl methacrylate, ethyl methacrylate, propyl methacrylate ester, butyl methacrylate, hexyl methacrylate, ethyl hexyl acrylate rylate, stearyl methacrylate and lauryl methacrylate are listed. Ru. Advantageously from alkyl acrylates and/or alkyl methacrylates A mixture of n-butyl acrylate is used as component (bl), which is n-butyl acrylate. or t-butyl acrylate and/or n-butyl methacrylate or Contains at least 25% by weight of t-butyl methacrylate-1.

Component (b2) is copolymerized with (bl), (b3), (al) and (a2). is possible, has at least one hydroxyl number per molecule, and has an essentially carbon All ethylenically unsaturated monomers without carboxyl groups or such monomers Mixtures of the following may also be used. Examples include acrylic acid, methacrylic acid or is another hydroxyalkyl ester of α,β-ethylenically unsaturated carboxylic acid be done. This ester is derived from an alkylene glycol that has been esterified with an acid. or the ester can be derived from the reaction of an acid with an alkylene oxide. Therefore, it can be obtained. Component (b2) is preferably a hydroxyalkyl group. Hydroquinoalkyl acrylic and methacrylic acids having up to 4 carbon atoms Esters include cyclic esters, such as ε-caprolactone and the hydroquinones mentioned above. Alkyl ester Tell A reaction product from a mixture of quinine alkyl esters is used. this kind of Examples of hydroxyalkyl esters include 2-hydroxyethyl acrylate , 2-hydroquinopropyl acrylate, 3-hydroquinopropyl acrylate , 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate. Also, another unsaturated Acids such as ethacrylic acid, crotonic acid and up to about 6 carbon atoms per molecule Corresponding esters of similar acids with esters may also be used.

Component (b3) is copolymerized with (bl), (b2), (al) and (a2). Possible, essentially free of carboxyl groups, different from (bl) and (b2) All ethylenically unsaturated monomers or mixtures of such monomers may be used. It's okay. Component (b3) is preferably a vinyl aromatic hydrocarbon, such as a styrocarbon. Polyols, α-alkyl styrenes and vinyldolols are used.

The polyacrylate resin used according to the present invention has a component (al) of 2.5 to 15% % by weight, preferably from 3 to 7% by weight, component (a2) from 0 to 60% by weight, preferably from 0 to 28% by weight. % to an organic solvent or solvent mixture where at least one polymerization Polymerization in the presence of an initiator and after the end of the addition of components (al) and (a2) the components Component (b) consisting of (bl), (b2) and optionally (b3) is dissolved in an organic solvent. agent or solvent mixture and therein a small amount (in the presence of at least one polymerization initiator) It can be produced by polymerizing. When adding component (b) contains components (al) and (a2) at least 60% by weight, advantageously less (both 80%) It is only started when the weight percentages have been converted.

When component (b) is added, components (al) and (a2) are essentially completely converted. It is advantageous to start for the first time when After the termination of the polymerization, the obtained The polyacrylate resin is at least partially neutralized and dispersed in water. Ru. The total weight of (al), (a2), (bl), (b2) and (b3) is , always 100% by weight. Ingredients (al), (a2), (bl), (b2) and and (b3), in terms of type and amount, the polyacrylate resin is O~200, especially Hydroxyl number of 20-120, acid number of 20-100, especially 25-50 and Has a glass transition temperature (To) of 40°C to +60°C, especially -20°C to +40°C selected as follows.

(al) and (a2) for preferably 10 to 90 minutes, particularly preferably 30 to 75 minutes is added to an organic solvent or solvent mixture in which at least one free radical is polymerized in the presence of a polymer-forming initiator. Component (b) is preferably added for 2 to 8 hours, especially It is added to the organic solvent or solvent mixture within 3 to 6 hours, where at least one The compounds used according to the invention are also polymerized in the presence of a free radical-forming initiator. The polyacrylate resin contains (al) and (a2) and component (b) in partial amounts. to the organic solvent or solvent mixture, where at least one free It can also be obtained by polymerization in the presence of a radical-forming initiator. in this case , the partial amount is the total of components (al) and (a2) or component (b), respectively. It consists of at least 10% by weight of the amount to be used. When adding partial quantities, at least 60% by weight, preferably at least 80% by weight, have been reacted. is started for the first time. When adding a portion, the preceding portion is essentially complete. It is advantageous to start only when the reaction has been completed. After termination of polymerization, The resulting polyacrylate resin has a low (and partially neutralized) content in water. be scattered. (al), (a2), (bl), (b2) and (b3) by weight The sum is always 100% by weight. Components (al), (a2), (bl), (b2 ) and (b3), the polyacrylate resin is 0 to 200% in terms of type and amount. , especially hydroxyl numbers between 20 and 120, acid numbers between 20 and 100, especially between 25 and 50. and -40°C to +60°C, especially -20°C to +40°C glass transition temperature (Ta ).

, in one preferred embodiment of this production method, in the first step component (b) 30 to 70%, preferably 40 to 60%, particularly preferably 30 to 70% by weight of the total amount to be used A portion (portion 1) of component (b) consisting of 50% by weight is an organic solvent or a solvent mixture. added to the compound and in the presence of at least one free radical formation initiator. will be combined. After the end of the addition of portion 1, in a second step mixing (al) and (a2) 30 to 70% by weight, preferably 40 to 60% by weight of the total amount to be used, in particular The partial amount (partial amount 2) of the mixture of (al) and (a2) consisting of 50% by weight is , added to the organic solvent or solvent mixture, and at least one free-rancal Polymerized in the presence of a forming initiator. After the end of the addition of portion 2, in a third step the components (b) from 30 to 70% by weight, preferably from 40 to 60% by weight of the total amount to be used, in particular A portion (portion 3) of component (b) preferably consisting of 50% by weight is an organic solvent or is added to the solvent mixture and in the presence of at least one free radical forming initiator. polymerized in the presence of After the end of the addition of portion 3, in a fourth step (al) and (a2) 30-70% by weight, preferably 40-60% by weight of the total amount to be used of the mixture with , particularly preferably 50% by weight of a mixture of (al) and (a2) Quantity 4) is added to the organic solvent or solvent mixture and contains at least one free Polymerized in the presence of a radical-forming initiator.

When adding portions 2.3 and 4, each preceding portion of at least 60 It is started only when % by weight, preferably 80% by weight, has been reacted. portion size Starts only when the preceding portion has essentially completely reacted upon addition After termination of the polymerization, the polyacrylate resin obtained has a small (both partially neutralized and dispersed in water. (al), (a2), (b The sum of the weight needles l), (b2) and (b3) is always 100% by weight. Growth Minutes (al), (a2), (bl), (b2) and (b3) are types and amounts. In this point, the polyacrylate resin has a hydroxyl number of O to 200, especially 20 to 120. , an acid number of 20 to 100, especially 25 to 50 and -40°C to +60°C, especially -20°C. It is selected to have a glass transition temperature (T, ) between 0C and +40C.

The addition of portions 1 and 3 is preferably carried out within 1 to 4 hours, particularly preferably between 11/2 and 3 hours. It is done. The addition of portions 2 and 4 is preferably carried out over a period of 5 to 30 minutes, particularly preferably between 7 and 30 minutes. It will take 20 minutes.

As an organic solvent and polymerization initiator, it is commonly used in the production of polyacrylate resin. In addition, suitable solvents and polymerization initiators may be used for preparing the aqueous dispersions. use Examples of possible solvents include butyl glycol, 2-methoxypropanol, n- Butanol, methoxybutanol, n-propanol, ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, ethylene glycol Monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Recol monoethyl ether, diethylene glycol noethyl ether, diethyl Len glycol monobutyl ether and 3-methyl-3-methquine butanol is described. Examples of polymerization initiators that can be used include free radical forming initiators , such as benzoyl peroxide, t-butylperethylhexanoate, azobisulfur Sobutyronitrile and t-butyl perbenzoic acid are mentioned. Polymerization is preferably is carried out at a temperature of from 80 to 160°C, preferably from 110 to 160°C. Polymerization is Termination is reached when all monomers used have been essentially completely reacted.

Components (al), (a2), (bl), (b2) and (b3) are types and amounts. in that the reaction product has a hydroxyl number of O to 200, preferably 20 to 120, 20 -100, preferably from 25 to 50 acid number and from -40°C to +60°C, preferably -20°C It is selected to have a glass transition temperature (To) of ~+40°C.

The glass transition temperature of polyacrylate resin can be calculated by the following formula: Ru.

Tc - glass transition temperature X of polyacrylate resin = polyacrylate resin Number of various monomers polymerized into W, = Weight percentage of nth monomer To6 = glass transition temperature of homopolymer of nth monomer The amount of initiator and the rate of addition are advantageously such that the amount of polyacrylate resin obtained is 250 It is controlled to have a number average molecular weight of 0 to 20,000. Polymerization addition of initiator Starting at the same time as the addition of possible components (al), (a2) and (b), e.g. Completed in 30 minutes after completion of addition of polymerizable components (al), (a2) and (b) It is advantageous to do so. Thereafter, the reaction mixture is essentially free of all monomers used. further maintained at the polymerization temperature until completely reacted (usually about 1.5 hours) be done. “Essentially completely reacted” means that the monomers used are advantageously This means that 100% by weight of the reaction mixture is reacted; A low residual monomer content of up to about 0.5% by weight based on the weight of the material can be used without reaction. It also means that it is possible to remain as is.

After completion of the polymerization, the polyacrylate resin obtained is at least partially neutralized. and dispersed in water.

For neutralization, organic as well as inorganic bases may be used. Advantageously, the first Primary, secondary and tertiary amines such as ethylamine, propylamine, di Methylamine, dibutylamine, nochlorohexylamine, benzylamine, mole Holin, piperinone and triethanolamine are used. Particularly advantageously, Tertiary amines, especially dimethylmethanolamine, triethylamine, tripropylene Ruamine and tributylamine are used as neutralizing agents.

Generally, the neutralization reaction is carried out by mixing the neutralized base with the polyacrylate resin. administered. In this case, the base lacquer is preferably from 7 to 85, preferably from 72 to 7. A large enough amount of base is used to have a pH value of 8.

Subsequently, the partially or completely neutralized polyacrylate resin is treated by adding water. It is dispersed. In this case, an aqueous polyacrylate resin dispersion is produced. . Optionally, some or all of the organic solvent can be distilled off. Main departure The polyacrylate resin dispersion according to Ming. contains polyacrylate lubricant particles, Its average particle size is advantageously between 60 and 300 nm (measurement method - laser light scattering method , Measuring instrument: Malvern Aut.

5izer 2C).

Using the polyacrylate resin described above as a binder, aqueous basecoat lacquer according to the invention can be prepared. A car can be manufactured.

However, the polyacrylate resin may be combined with at least one water diluted resin as a binder. water dilutable polyurethane resin and/or less (both one water dilutable polyurethane resin) a stell resin and/or at least one water-dilutable aminoblast resin; A combination is advantageous. Only non-metallic pigments or non-metallic pigments are used. In the case of base lacquers containing only a mixture of pigments and no metallic pigments, , advantageously, (A) 10 to 95% by weight of water-dilutable polyacrylate resin according to the invention, advantageously 25 to 70% by weight, (B) aminoplast resin 5 to 50% by weight, preferably 10 to 70% by weight. 40% by weight, (C) Water-dilutable polyester resin 0-85% by weight, preferably 20-60% by weight , (D) Water-dilutable polyurethane resin 0-85% by weight, preferably 0-40% by weight A mixture consisting of is used.

The sum of the weight proportions of components (A) to (D) is always 100% by weight.

Metallic pigments or mixtures of metallic pigments, optionally in combination with non-metallic pigments. In the case of base lacquers contained in combinations, (A) the present invention is advantageously used as a binder. 0.1 to 60% by weight of water-dilutable polyacrylate resin according to the invention, preferably 1 to 3% by weight 0% by weight, (B) aminoblast resin 0-50% by weight, preferably 50-30% by weight , (C) Water dilutable polyester resin O-5 (Lt-1%, preferably 15-40 wt. amount%, (D) Water-dilutable polyurethane resin 10-99.9% by weight, preferably 20-60% weight% A mixture consisting of is used.

The sum of the weight proportions of components (A) to (D) is always 100% by weight.

The polyacrylate resin described above and, for example, (i) a number average molecular weight of 400 to 5000. of polyester and/or polyether polyols or such Mixtures consisting of polyester polyols and/or polyether polyols (11) a mixture consisting of polyisonnanate or polyisocyanate; (ii) at least one substance reactive with isocyanate groups in the molecule; Compounds having at least one group capable of forming a reactive group and an anion or a mixture of such compounds, (iv) optionally from 40 to 60 Hydroxyl and/or amino group-containing organic compounds having a molecular weight of 0 or is a mixture of such compounds; (v) optionally contains NGOs in the molecule; at least one group reactive toward the group and at least one poly(oxyamine) group. Compounds containing (alkylene) groups or mixtures of such compounds react with each other, and the resulting reaction products are small (and partially neutralized). may be combined with water-dilutable polyurethane resins that can be produced by Po The urethane resin preferably has an acid value of 10 to 60 and an acid value of 4000 to 25000. It has a number average molecular weight.

Polyurethane resins include (1), (11), (iii), and in some cases (iv) and optionally from (V), those familiar to those skilled in the art of polyurethane chemistry. Vine produced by a method (e.g., U.S. Pat. Federal Republic of Patent Application No. 3628124, European Patent Application No. 894 Specification No. 97, European Patent Application Publication No. 256540 and International Publication Number (See WO87103829).

Component (i) includes saturated and unsaturated polyester polyols and/or Polyether polyols, especially polyethers with a number average molecular weight of 400 to 5000 Sterdiols and/or polyether diols may also be used. suitable For example, the polyether diol has the general formula: H(-0-(CHR') n- ) In the moHC formula, R1 is a hydrogen atom or a lower optionally substituted alkali kill group, n is from 2 to 6, preferably from 3 to 4, and m is from 2 to 100. advantageously 5~ 50]. Examples include linear or Molecular chain polyether diols, such as poly(oxoethylene) glycol, Poly(oxypropylene) glycol and poly(oxybutylene) glycol be written. The selected polyether diol introduces an excess amount of ether groups. There shouldn't be any. This is because the polymers formed usually swell in water. It is from. Preferred polyether diols have a molecular weight range M of 400 to 3000 , poly(oxypropylene) glycol.

Polyester diol is an organic dicarboxylic acid using an organic diol or its absence. produced by esterification of water or hydroquinocarboxylic acids or Derived from tons. In order to produce molecular chain polyester polyol, Polyols or polycarboxylic acids with higher valences are used on a small scale. It's okay. Dicarboxylic acids and diols are linear or molecular chain aliphatic, cycloaliphatic or an aromatic dicarboxylic acid or diol.

Diols used for the production of polyesters include, for example, alkylene glycols. such as ethylene glycol, propylene glycol, butylene glycol, Butanediol-1,4, hexanediol-1゜6, neopentyl glycol and another diol, such as dimethylolnochlorohexane. However, Additionally, small amounts of polyols such as trimethylolpropane, glycerin, and Litrinoto may also be added. The acid component of polyester is primarily composed of carbon in the molecule. low molecular weight dicarboxylic acids having 2 to 30 atoms, preferably 4 to 18 atoms; Consists of anhydrous substances. Suitable acids are, for example, 0-phthalic acid, isophthalic acid, terephthalic acid. Acid, tetrahydrophthalic acid, noclohexanedicarponic acid, succinic acid, adipic acid , azelaic acid, sebacic acid, maleic acid, fumaric acid, glutaric acid, hexachloro Ruheptanedicarboxylic acid, tetrachlorphthalic acid and/or dimeric fatty acids It is. Instead of the aforementioned acids, their anhydrides can be used if this anhydride is present. You may. In the case of forming polyester polyols, three or more Smaller amounts of carboxylic acids with carboxyl groups, such as trimellitic anhydride or An adduct of maleic anhydride may be present in the unsaturated fatty acid.

Polyester diols obtained by the reaction of lactones and diols are used. It's okay. This has the terminal hydroxybutyric acid and the formula (-CO-(CHR”)n -CH20) is notable for its repeating polyester component. in this case , n is preferably 4 to 6, and the substituent R2 is a hydrogen atom, an alkyl group, a cycloatom It is an alkyl group or an alkokino group.

Substituents have up to 12 carbon atoms. The total number of carbon atoms in the substituents is easily determined. No more than 12 pieces per tonne ring. An example for this is hydroquinocaproic acid , hydroxybutyric acid, hydroxydecanoic acid and/or hydroquinostearic acid It is.

For the production of polyester diols, n has a value of 4 and all R substituents are hydrogen. Preference is given to atomically unsubstituted ε-caprolactone. Reaction with lactones is a low molecular weight polyol, such as ethylene glycol, 1,3-propane starting with alcohol, 1,4-butanediol, dimethylolnochlorohexane be able to. But also other reaction components, e.g. ethylenediamine, alkyl The dialkanolamine or also the urea may be reacted with caprolactone.

Component (ii) may include aliphatic and/or alicyclic and/or aromatic polycarbons. Liisocyanates may also be used. Examples of aromatic polyisonoanates include , phenylene diisocyanate, toluylene diisocyanate, quinolylene diisocyanate socyanate, biphenylene diisocyanate, naphthylene diisocyanate and and nophenylmethane isonoanaate.

Due to its good stability against ultraviolet light, it has a slight tendency to yellowing ( b) An aliphatic polyisocyanate product is formed. An example for this is isophorone di Isocyanates, cyclopentylene diisocyanates and aromatic diisonores Hydrogenation products of esters, such as cyclohexene diisocyanate, methylcyclo dichlorohexylene diisonoate and zinclohexolmethanoate It is. The colloquial aliphatic diisonoanate has the formula %formula% [In the formula, r is an integer of 2 to 20, especially 6 to 8, and R3 is the same or different hydrogen atoms or 1 to 8 C atoms, preferably 1 or 2 C atoms. represents a lower alkyl group having the following formula. An example for this is Methylene diisocyanate, tetramethylene diisocyanate, pentamethylene Diisocyanate, hexamethylene diisocyanate, propylene diisocyanate ethyl ena diisocyanate, dimethyl ethylene diisonoanate, Methyl trimethylene diisocyanate and trimethylhexane diisocyanate It is. Isophorone diisocyanate is particularly preferably used as diisocyanate. and dicyclohexylmethane diisoocyanate are used.

Component (ii) is a crosslinked polyurethane with respect to the functionality of the polyisocyanate. The structure must be such that no resin is obtained. This component (i i) is a diisocyanate as well as a polyisocyanate having a functionality of 2 or more. It may also contain a content of, for example, triisocyanates.

As triisocyanates, trimerization or oligomerization of diisocyanates or with diisocyanate and polyfunctional OH or NH groups. Products formed by reaction with compounds have proven advantageous. to this For example, hexamethylene diisocyanate and water biuret, hexamethylene diisocyanate Isocyanate of diisocyanate or isophorone diisocyanate? This includes adducts to trimethylolpropane. Average sensuality is sometimes The vines are reduced by the addition of monoisonoanate. Things like this that stopped the chain Examples of isonanoates are phenyl isocyanate, cyclohexyl isocyanate and stearyl isonanoate.

Forming anions to ensure the water dilutability of the polyurethane resin used A group having the ability to do so must be incorporated into the polyurethane molecule. Yin Yi The group having the ability to form a ion, after its neutralization, makes the polyurethane resin stable in water. It is useful for making it possible to decentralize and decentralize. Polyurethane resin is 10-60, It has an acid value of 20 to 35. From this acid value, it has the ability to form anions. The amount of the group to be introduced into the polyurethane molecule can be calculated.

The introduction of a group capable of forming anions into the polyurethane molecule allows the compound ( This is done by incorporating i　i　i).

As component (ii), advantageously there are two reactivity towards isocyanate groups. A compound having the group in the molecule is used. suitable for reactivity towards isocyanate groups. Suitable groups are in particular hydroxyl groups and primary amino groups and/or secondary amino groups. It is a mino group. Suitable groups having the ability to form anions include carboxyl groups, A sulfonic acid group and/or a phosphonic acid group, in which case the carboxyl group is It's advantageous. As the component (ii), for example, two substitutions at the α-position carbon atom Alkanoic acids having groups may also be used. This substituent is a hydroxyl group, a It may be an alkyl group or preferably an alkylol group. This alkanoic acid is less Both have one, generally 1 to 3 carboxyl groups in the molecule. This is carbon It has from 2 to about 25 atoms, preferably from 3 to 10 atoms. An example of component (ii) is di Hydroxypropionic acid, dihydroxysuccinic acid and dihydroxybenzoic acid. Ru. Particularly advantageous groups of alkanoic acids have the general formula R'C(CH20H)2CO In the OHC formula, R4 represents a hydrogen atom or an atom having up to about 20 carbon atoms. represents an α,α-dimethylol alkanoic acid. like this Examples of such compounds are 2,2-dimethylol acetic acid, 2,2-dimethylol propion acids, 2,2-dimethylolbutyric acid and 2,2-dimethylolpencuic acid.

A preferred dihydroxyalkanoic acid is 2,2-dimethylolpropionic acid.

Examples of amino group-containing compounds include α,δ-diaminovaleric acid, 3,4-diaminoben Froic acid, 2,4-diaminodololsulfonic acid and 2,4-diamino-dife Nyl ether sulfonic acid.

The polyurethane resin used according to the invention optionally has a Hydroxyl group-containing and/or amino group-containing organic compound or can be prepared in combination with a mixture of such compounds (component (i) v)). The use of component (1v) results in an increase in the molecular weight of the polyurethane resin.

Component (iv) may be, for example, a polyol having 20 carbon atoms per molecule. such as ethylene glycol, diethylene glycol, triethylene glycol 1,2-butanediol, 1,3-protZol, 1,4-butanediol ol, 1,2-butylene glycol, 1,6-hexanediol, trimethyl castor oil or hydrogenated castor oil, di-trimethylol propane Panether, pentaerythritol, 1,2-cyclohexanediol, 1,4 -Cyclohexane dimethanol, bisphenol A, bisphenol F1 Opentyl glycol, hydroxypivalic acid neopentyl glycol ester , hydroxyethylated or hydroxypropylated bisphenols Even if hydrogenated bisphenol A and mixtures thereof are used good.

The polyol is generally 30% by weight based on the amounts used of components (i) and (iv). % by weight, preferably from 2 to 20% by weight. As component (iv), Dipolyamine and/or having a primary amino group and/or a secondary amine group Polyamines may also be used. Polyamines essentially contain 1 to 40 carbon atoms. , preferably 2 to 15 carbon atoms, e.g. . The polyamine has hydrogen atoms that have the ability to react with isocyanate groups. can have no substituents. Examples are linear or branched aliphatic, cycloaliphatic or a polyamine having an aromatic structure and at least two primary amino groups It is. Diamines include hydrazine, ethylene diamine, and propylene diamine. 1,4-butylene diamine, piperazino, 1,4-cyclohexylcythyl Amine, hexamethylenediamine-1,6, trimethylhexamethylenediamine , menthanediamine, isophoronediamine, 4,4'-diaminodicyclohexy lumethane and aminoethylethanolamine. Advantageous diamines are , hydrazine, alkyl diamines or cycloalkyl diamines, such as propylene Diamine and 1-amino-3-amino-methyl-2,5,5-trimethyl It is cyclohexane.

Polyamine is used as component (iv) having two or more amino groups in the molecule. You may be However, in the above case, e.g. by co-use of monoamines, , care must be taken not to obtain a crosslinked polyurethane resin. child Possible polyamines such as diethylenetriamine, triethylenetetra amine, dipropylenetriamine and diethylenetriamine. Monoamine As an example, ethylhexylamine is mentioned.

Using component (V), the poly(oxyalkylene) group is a nonionic stable group. It may also be introduced into the polyurethane molecule as a polyurethane molecule. As component (V), for example, General formula: R'O-(-CH2-CHR''-0-)H [wherein, R' is a carbon atom represents an alkyl group having 1 to 6 atoms, and R' represents a hydrogen atom or a carbon atom. represents an alkyl group having 1 to 6 children, n represents a number of 20 to 75] Alkoxypoly(oxyalkylene) alcohols may also be used.

Polyurethane resins usable in combination with the essential polyacrylate resins of the invention The production of fats belongs to the state of the art, for example US Pat. No. 4,719,132; German Patent Application No. 3628124, European Patent Application No. 8 No. 9497, European Patent Application No. 256450 and International Publication No. It is described in detail in No. WO87103829.

Water-dilutable polymers usable in combination with the essential polyacrylate resins of the present invention Urethane resins are generally made from polycarboxylic acids and polyols (known as It can be manufactured by a method. For the production of polyester resin, component (i ) can be used.

Polyester resins are preferably used as water-dilutable polyester resins, this is, (α) polyol or mixture of polyols, (β) polycarboxylic acid or is polycarboxylic anhydride or polycarboxylic acid and/or polycarboxylic acid The mixture of anhydrides is added to a number of 600-500.0, preferably 800-2500 average molecular weight of 20 to 70, preferably 25 to 55 and an acid number of 30 to 200, preferably 4 Converted to a polyester resin with a hydroxyl number of 5 to 100, in this case: - components (α) and (β) are between 1.15 and 2,001, preferably between 1.2 and 15:1; -component (α) is used in a molar ratio of 30 to 100 mol% as secondary, secondary Aliphatic with at least one α-C atom that is a member of a tertiary or carbon-containing ring system -component (β) consists of 50 to 100 mol% of aromatic and / or alicyclic polycarboxylic acid, and up to 15 to 40 mol% is tricarboxylic. tricarboxylic acid and or tetracarboxylic acid, in this case tricarboxylic acid and / or tetracarboxylic acid, which is present through at least two carboxyl groups , obtained by being used to be incorporated into polyester resin molecules .

The component (α) is (α1) 30 to 100 mol%, preferably 50 to 100 mol%, of secondary, tertiary or or aliphatic diol having at least one α-C atom that is a member of a carbon-containing ring system. Consisting of (α2) 0 to 20 mol%, preferably 0 to 10 mol%, of aliphatic triols , (α3) 0 to 40 mol%, preferably 0 to 20 mol%, is an ether group-containing diol It will be.

In principle, the component (α1) contains 4 to 40 carbon atoms, preferably 5 to 1 carbon atoms in the molecule. All aliphatic diols having two can be used, in which case there are fewer (both one α -C atom is a secondary or tertiary C atom or a member of a carbon atom-containing system. Also , mixtures of such diols may also be used. As the (α1) component, for example, General formula: C(R”R2)-CH20H (wherein R1 and R2 are 1 carbon atom represents an aliphatic, cycloaliphatic or aromatic hydrocarbon radical having ~20, preferably 1 to 6 Compounds having at least one molecular fragment shown in be. Examples of compounds of this type include neopentyl glycol, 2-methyl-2 -Propylpropanediol-1,3,2-ethyl-2-butylpropanediol Ru-1,3,2-ethyl-2-phenylpropanediol-1,3,2,2,4 Trimethylpentanol 1.5.2.2.5 Trimethylhexanediol 1.6 and hydroxypivalic acid neopentyl glycol ester are described. It will be done. Compounds in which at least one α-C atom is a member in a carbon-containing ring system As an example, dimethylolcyclohexane is mentioned. As component (α1) is advantageously neopentyl glycol, neopentyl glycohydroxypivalate ester, dimethylolcyclohexane and 2-ethyl-2-butyl pro- Pandiol-1,3 is used.

Examples of the component (α2) include glycerin, trimethylolpropane, and trimethylolpropane. Methylolethane may also be used.

Component (α3) is particularly suitable for dihydrogen having 1 to 10 ether oxygen atoms in the molecule. ols or mixtures of such compounds are used. Example of component (α3) The following are listed as diethylene glycol and dipropylene glycol. triethylene glycol, tripropylene glycol, tetraethylene glycol cole, tetrapropylene glycol and has a number average molecular weight of 400 to 600. poly(ethylene oxide), poly(propylene oxide) and poly(ethylene oxide) ) (propylene oxide).

The component (β) is (β1) 50 to 100 mol%, preferably 50 to 80 mol%, of aromatic and/or is a cycloaliphatic polycarboxylic acid or a mixture of such polycarboxylic acids, (β2 ) 0 to 50 mol%, preferably 20 to 50 mol%, of aliphatic polycarboxylic acids or fatty acids. Consisting of a mixture of aliphatic carboxylic acids, In this case, the content of tricarboxylic acid or tetracarboxylic acid is 15 to 40 mol% It is. Of course, instead of carboxylic acids, reactive carboxylic acid derivatives such as carboxylic acids can be used. Acid anhydride may also be used.

In principle, the component (β1) contains 5 to 30 carbon atoms, preferably 6 to 1 carbon atoms in the molecule. Any alicyclic or aromatic polycarboxylic acid or said polycarboxylic acid having 8 Anhydrides of acids or mixtures of the polycarboxylic acids or anhydrides thereof are used. may be done. Examples of polycarboxylic acids that can be used are isophthalic acid, terephthalic acid, Talic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 1. 4 cyclohexane dicarboxylic acid, dinoclopentadiene dicarboxylic acid, trimeno Trimellitic acid (benzo-1,3,5-tricarboxylic acid), trimellitic acid, pyromellitic acid and endomethylenetetrahydrophthalic acid and its anhydrides are described. Ru. Component (β1) is preferably isophthalic acid, tetraphthalic acid, orthophthalic acid. hydrochloric acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitrimellitate a mixture of the above-mentioned polycarboxylic acids or anhydrides; things are used.

In principle, the component (β2) is a linear or or a branched aliphatic polycarboxylic acid or an anhydride of said polycarboxylic acid, or Mixtures of the polycarboxylic acids or their anhydrides may also be used. messenger Examples of aliphatic polycarboxylic acids that can be used include oxalic acid, malonic acid, and succinic acid. , glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sepanonic acid , maleic acid, fumaric acid, polymerized fatty acids and citric acid and their anhydrides were recorded. It will be posted. As component (β2), advantageously adipic acid, azelaic acid, sepano from phosphoric acid, succinic acid, its anhydride, or the above polycarboxylic acid or its anhydride. A mixture of these is used. Component (β2) can be very particularly advantageously polymerized, especially Dimerized fatty acids are used. Polymerized fatty acid is used as component (β2) When used, base lacquers with particularly good storage stability are obtained.

That is, the fatty acid of the polymer is a fatty acid such as lylunic acid, linoleic acid or oleic acid. Acids can be polymerized alone, in mixtures, or in mixtures with saturated fatty acids. Therefore, it is manufactured. Depending on the performance of the reaction, dimers or alternatively monomers can be used as species. and trimer molecules as well as by-products. Amazingly, Purified by distillation. That is, the fatty acids of the commercially available polymers contain at least 80 dimers. % by weight, trimers up to 20% by weight and monomeric fatty acids up to 1% by weight.

At least 98% by weight of fatty acids are dimers and up to 2% by weight of trimers and most Using polymeric fatty acids as component (β2), consisting of large and trace monomeric fatty acids. It is advantageous to use

Polymeric fatty acids have cyclic as well as linear aliphatic molecular fragments. but However, in the sense of the present invention, the fatty acids are not as cycloaliphatic, but as linear It is considered an aliphatic polycarboxylic acid and is therefore added to component (β2).

Tricarboxylic or tetracarboxylic acids are preferably trimellitic acid or or pyromellitritic acid, mixtures thereof or anhydrides thereof.

The production of water-dilutable polyester resins is a generally well-known part of polyester chemistry. It is carried out by the reaction of components (α) and (β) according to the method described above. The reaction temperature is , preferably from 140 to 240°C, advantageously from 180 to 220°C. In many cases It is preferable that the esterification reaction be promoted. Examples of catalysts that can be used are tet butyl titanate, zinc octoate, tin octoate, dibutyltin oxide, di Organic salts of butyltin oxide, etc. In case of esterification, tricarboxylic acids or a tetracarboxylic acid with at least two carboxyl groups by statistical means. It should be noted that it is incorporated into the polyester resin molecule so that it is stellated. be.

For neutralization of polyester resins, dark spots and/or amines (in particular amines) are used. aminoalcohols and cyclic amines, such as diethylamine and and triethylamine, dimethylaminoethanolamine, diisopropanol Amines, morpholines, N-alkylmorpholines, etc. may be used. For neutralization For this purpose, readily volatile amines are advantageous.

Aminoplasts usable in combination with the essential polyacrylate resins of the invention Resins are offered commercially by many companies (e.g. American C of AIIerican Cyanamid Company ymel®, Monsanto Company (Mon5ant.

Company) Res imene (registered trademark), Peeninisf Company ( Luwipal® from BASF AG). Usually a compound containing an amino group , such as maleic or pentuguanamine and aldehydes, especially formaldehyde. Hido is important. In general, the water dilutability of aminoplast resins depends on the concentration ratio and and etherification components. Low concentration in the etherification component and a The shorter the alkyl group is, the more water-dilutable the aminoblast resin becomes. performance is good. In addition, the water dilutability of aminoblast resin is Improvements can be made by introducing groups (e.g. etherification using hydroxycarboxylic acids). You can also

Additionally, the water dilutability of aminoblast resins is limited by water dilutable solvents such as glycosyl This can be improved by adding alcohol ether.

Together with the abovementioned binders, the base lacquer according to the invention can be used for compounding pigments and and/or contain further water-dilutable synthetic resins that serve as rheological control additives. can do. Examples of this type of synthetic resin include: riethers, e.g. polypropylene with a number average molecular weight of 400 to 900 recalls, water-soluble cellulose ethers such as hydroxyethyl cellulose, Chillulose or carboxymethylcellulose and ionic and/or is a synthetic polymer having an associatively acting group, such as polyvinyl alcohol, poly (meth)acrylamide, poly(meth)acrylic acid, polyvinylpyrrolidone, Styrol-maleic anhydride-copolymers and their derivatives or also hydrophobic Modified ethylated urethane or carboxyl group-containing polyacrylate.

The base lacquer according to the invention can also be used, for example, as disclosed in European Patent Application No. 38127 It may also contain crosslinkable polyparticles as disclosed in the specification.

The basecoat lunker according to the invention also contains an inorganic rheological control agent, such as a layered silicate. May be contained.

As pigments, the base lacquers according to the invention may be based on inorganic bases, such as titanium dioxide. , colored pigments and/or organic substrates based on iron oxides, carbon blanks, etc. colored pigments and/or conventional metal pigments (e.g. commercially available aluminum bronze, steel bronze, etc.) and/or non-metallic effect pigments (e.g. pearlescent pigments). or interference pigments). The base lacquer according to the invention It preferably contains metal pigments and/or effect pigments. Pigmentation height is in the normal range It is within.

The base lacquer according to the invention generally has a spraying viscosity of about 15 to 50% by weight. It has a solids content of . The solids content varies with the intended use of the base lacquer.

For metallic lacquers, the solids content is, for example, preferably from 17 to 25% by weight. single For colored lacquers, the solids content is higher, for example 30-45% by weight. Ru.

The base lacquer according to the invention can additionally contain customary organic solvents. . Its content is kept as low as possible. This is, for example, less than 15% by weight. be.

Generally, the base lacquer according to the invention is adjusted to a pH value between 65 and 9.0. . This pH value is the same as that of commonly used amines, such as triethylamine and dimethylamino. can.

The base lacquer according to the invention can be used in continuous coating applications (two-part refinish coatings). be able to. The base lacquer is preferably used in continuous application.

As clear topcoat lacquers, lacquers based on organic solvents, water-dilutable lacquers, etc. Cars and powder lacquers may also be used.

In addition, if the base lacquer according to the present invention is used, it may be repainted with a transparent top lacquer. It is also possible to produce coatings of high quality without the need for this process. Thus, especially high light The lacquer according to the invention, which gives a pronounced monolayer coating by coating, can be used on any support. , for example on metal, wood, synthetic resin or paper.

The invention will be explained in detail in the following examples.

All references to parts and percentages refer to parts and percentages unless explicitly stated otherwise. is the weight display.

A1 Production of polyacrylate resin to be used according to the invention Steel with monomer feed tube, initiator feed tube, thermometer, oil heater and reflux condenser 32 parts by weight of butyl glycol was charged into the kettle and heated to 110°C.

Then t-butylberethylhexanoate in 3.5 parts by weight of butyl glycol The 156 parts by weight solution was added at such a rate that the addition was complete after 1 hour and 30 minutes. added. At the beginning of the addition of t-butylperethylhexanoate solution, (al) 56 parts by weight of acrylic acid and 3.1 parts by weight of (a2) nibutyl methacrylate, 1.96 parts by weight of methyl methacrylate and 393 parts by weight of lauryl methacrylate The addition of the mixture consisting of 196 parts by weight and 196 parts by weight of styrene is started at the beginning.

The mixture consisting of (al) and (a2) is heated to such an extent that the addition is complete after 1 hour. added at a rate of

After the t-butylperethylhexanoate solution is completely added, the polymerization temperature is , and maintained at 110° C. for an additional 30 minutes.

Next, t-butylperethylhexanoate in 6.0 parts by weight of butyl glycol 6.0 parts by weight of the solution was added at such a rate that the addition was complete after 5 hours and 30 minutes. added.

Start of addition of t-butylperethylhexanoate solution, (bl)・n-butyl 21°6 parts by weight of methyl methacrylate, 20.0 parts by weight of methyl methacrylate and 200 parts by weight of lauryl methacrylate, (b2): hydroxypropyl acrylate of a mixture consisting of 20.4 parts by weight of salt and 150 parts by weight of (b3) nistyrol Addition is also started at the same time. A mixture consisting of (bl), (b2) and (b3) is added at such a rate that the addition is complete after 5 hours.

The temperature is maintained at 110° C. for an additional 1 hour and 30 minutes. The resin solution obtained in this way The liquid was concentrated to 80% by weight (solids content) by distillation under vacuum and dimethyl ethanol. Neutralized using Ruamine at about 80°C for about 30 minutes to a neutralization rate of 80%. Ru. The resin solution is cooled to 60° C. and the heater is turned off.

Subsequently, water is slowly added in an amount until the solids content of the dispersion is approximately 40% by weight. It will be done.

The obtained dispersion has the following index: acid value KOH 32.8 mg/g, hydroxide Roxyl number: 80, number average molecular weight: 4990, particle size: 221 nm Laser light scattering method , was measured using a measuring instrument Malvern Autosizer 2C.

Steel with monomer feed tube, initiator feed tube, thermometer, oil heater and reflux condenser 358 parts by weight of butyl glycol are charged into the kettle and heated to 110°C. Next 35 parts by weight of t-butylperethylhexanoate in 70 parts by weight of butyl glycol. Parts by weight of the solution are added at such a rate that the addition is complete after 5 hours and 30 minutes. Ru.

At the beginning of the addition of t-butylperethylhexanoate solution, (al)niacryl Addition of 50 parts by weight of acid is started at the beginning. (al) is completed after 20 minutes of addition. It is added at such a rate that After (al) is completely added, (bl )・220 parts by weight of n-butyl acrylate, 20°0 parts by weight of t-butyl acrylate parts and 150 parts by weight of methyl methacrylate, (b2) hydroxypropylene 23.0 parts by weight of acrylate and (b3) 15.0 parts by weight of styrene. From Ot part 1 The mixing process starts. A mixture consisting of (bl), (b2) and (b3) is The rate of addition is such that the addition is complete after 4 hours and 50 minutes.

After the mixture consisting of (bl), (b2) and (b3) has been completely added, warm The temperature is maintained at 110° C. for an additional 1 hour and 50 minutes.

The resin solution thus obtained was cooled to 80°C and dimethylethanolamine was added. Neutralization is carried out at about 80° C. for about 30 minutes to a neutralization rate of 825%.

The resin solution is cooled to 60°C and the heater is turned off.　Subsequently, the solid of the dispersion Water is added slowly in an amount until the content is about 40% by weight.

The resulting dispersion had the following index: acid value KOH 33.5 mg/g1 hydride. Roxyl number = 100, particle size 267, solids content (% by weight, 1 hour at 130 °C): 40.0° B9 Production of polyacrylate resin not according to the present invention Monomer supply pipe, initiator supply pipe , butyl glycol 3 in a steel kettle equipped with a thermometer, oil heater and reflux condenser. 5.8 parts by weight are charged and heated to 110°C. Next, butyl glycol 7. A solution of 35 parts by weight of t-butylperethylhexanoate in 0 parts by weight is The addition is done at such a rate that it is complete after 5 hours and 30 minutes.

At the beginning of the addition of the t-butylperethylhexanoate solution, the n-butyl methacrylate 220 parts by weight of t-butyl acrylate, 200 parts by weight of t-butyl acrylate, methyl methacrylate 150 parts by weight of styrene, 150 parts by weight of styrene, hydroxypropyl acrylate The addition of the mixture consisting of 230 parts by weight and 50 parts by weight of acrylic acid starts at - be done.

The monomer mixture is added at such a rate that the addition is complete after 5 hours and 10 minutes. Ru.

Other treatments are the same as A2.

The obtained dispersion has the following indexes: acid value KOH 39, Omg/g, hydroxide Roxyl number, 100, solids content (wt%, 1 hour, at 130°C): 400° C Production of aqueous polyurethane resin dispersion Polymeric fatty acids (dimer content of at least 98% by weight, at most 3% by weight) 1 mol of isophthalic acid (monomer content, at most trace monomer content), 1 mol of isophthalic acid and Condensation product (number average molecular weight: 1460) consisting of 2626 moles of sandiol 5 69 parts by weight, 46 parts by weight of dimethylolpropionic acid, 7 parts by weight of neopentyl glycol parts by weight, 420 parts by weight of methyl ethyl ketone and 2 parts by weight of isophorone diisonoanate 13 parts by weight in a temperature adjustable reaction vessel equipped with a stirrer and a water separator. Heat to 80° C. under nitrogen atmosphere. The reaction was carried out using 1.0% by weight of the total composition. Performed up to NCO content. Next, 241 parts of trimethylolpropane was added. and stirred at 80° C. until no isonoanate groups are anymore visible.

Next, 25.8 parts by weight of dimethylethanolamine, followed by 2552 parts by weight of deionized water. Parts by weight are slowly added with stirring. Methyl ethyl ketone is distilled off under vacuum .

It has a pH value of 78, a non-volatile content of 27% by weight and an acid value of 25mg/g KOH. A finely dispersed dispersion is obtained.

D. Production of aqueous polyester resin dispersion Equipped with a stirrer, thermometer and packed distillation column In a reactor, 729 parts by weight of neopentyl glycol, hexanedio-/I/ 827 parts by weight, 462 parts by weight of hexahydrophthalic anhydride and polymeric fatty acid (dimer content of at least 98% by weight, trimer content of at most 2% by weight, at most 1710 parts by weight (with trace monomer content) are metered in and melted. While stirring The distillation column is heated to such an extent that the top temperature does not exceed 100°C. Maximum temperature 22 Esterification is carried out at 0° C. until an acid number of 8.5 is achieved. Cooling to 180℃ After cooling, 768 parts by weight of trimellidritic anhydride was added to achieve an acid value of 30. It is further esterified until Next, it was cooled to 120°C, and the butanol 1 It is dissolved in 410 parts by weight. After cooling to 90°C, dimethylethanolamine 1 6.2 parts by weight followed by 1248 parts by weight of deionized water are slowly added with stirring.

pH value of 7.8, non-volatile content of 60% by weight and acid value of KOH 30mg/g. A finely dispersed dispersion is obtained.

E. Production of water-based metallic undercoat lacquer (comparative example) 335 parts by weight of thickening agent (laminated structure Sodium-magnesium-silicate with *3% in water) is charged.

This was combined with 43 parts by weight of butyl glycol and a commercially available water dilutable solution in isobutanol. 90% solution of functional maleic-formaldehyde resin (Cymel 327) A solution consisting of 60 parts by weight of is added with stirring. Continue to this mixture , 33.3 parts by weight of the PUR dispersion described in C and a dimethylethanolamine solution 0.4 parts by weight (10% in H2O) are added with stirring. separate from this The aluminum pigment suspension is prepared as follows: commercially available chromate treatment 4.4 parts by weight of aluminum paste (benzine/solvent/butyl glycol) 65% in cole, average particle size: 15 μm), added 4 parts by weight of butyl glycol while it is being homogenized. Subsequently, the water-soluble polyester according to D is added to the suspension. 64 parts by weight of resin and 1.0 parts by weight of polypropylene glycol (number average molecular weight: 900) is added. The above mixture is added to this aluminum pigment suspension with stirring. be done. After this, 67 parts by weight of deionized water was added and trimethylethanolamine was added. The solution (10% in water) is adjusted to a pH value of 7.65-785.

* Laponite RD American Nanamid Co., Ltd. rica'n Cyanawid Company) products F0 Preparation of water-based metallic base lacquer according to the invention 335 parts by weight of thickening agent (laminated structure) Sodium-magnesium-silicate having a chemical composition (3% in water) is charged.

This was supplemented with 4.3 parts by weight of butyl glycol and a commercial water dilution in isobutanol. 90% dissolution of possible maleic-formaldehyde resin (Cymel 327) A solution consisting of 660 parts by weight of liquid is added with stirring. Continue with this mixture 33.3 parts by weight of the PUR dispersion described in C and dimethylethanolamine solution 4 parts by weight of liquid 0 (10% in water) and the polyacrylate resin dispersion described in A1 48 parts by weight of the liquid were added sequentially with stirring. Separately, aluminum face The suspension is prepared as follows. Commercially available chromated aluminum Paste 4.4 parts (65% in benzine/solvent/butyl glycol, The average particle size (15 μm) was made uniform by adding 4 parts by weight of butyl glycol. Ru.・Subsequently, 3.2 parts by weight of the water-soluble polyester resin described in D is added to the suspension. and 10 parts by weight of polypropylene glycol (number average molecular weight: 900). It will be done. The above mixture is stirred and added to this aluminum pigment suspension. After this, 38 parts by weight of deionized water was added and dimethylethanolamine solution (10 parts by weight in water) was added. %) to a pH value of 765-7.85.

* Laponite RDG water-based metallic undercoat lacquer application and waterborne metallic basecoat lacquers produced as described in Tests E and F. water, adjusted to 24.2% coating solids by weight, commercially available electrocoated coatings and commercially available fillers. The coating is applied to such an extent that a thin film thickness can be obtained by laminating layers. The applied base lacquer is , dried in a circulating air oven for 10 minutes at room temperature and 10 minutes at 80°C. next, A commercially available 2-clear lacquer is used under polyacrylate/polyisocyanate. applied on the ground, then briefly evacuated and placed in a circulating air oven at 140°C for 20 minutes. It is burned inside.

Test results/Described in E. Described in F Undercoat lacquer Undercoat lacquer L25° (1) 101.7 102.2L70' (1) 40,4 40 ．． 9 Gloss (2) 83 84 DOI (3) 92 92 Fundamentals exam (4) 00 by KK Gloss (5) 81 81 by K.K. Fundamentals Examination 11 DOI by KK 91 91 1) Color distribution according to DIN 617.4 * is the angle of change of Zeiss Measure with a spectrophotometer.

2) Brightness according to DIN 67530, angle 20° 3) Distinctness Distinctness of Refle ctedIsage): Directly in the case of illumination of the surface to be evaluated below 30° The reflection is -30° ± 0.3° in the immediate vicinity of the gloss angle -306 and gloss angle degrees. be measured. The DOI value measured from this is the mirror image of the object on said surface. It is consistent with the sharpness that was visually felt. Also, D.

The I value is also called an image sharpness value. Measured value: Best value 100: Minimum value 0° 4) DI including Tesa adhesive tape peel test (Te5aabriss-Test) Test according to N53151.

5) 240 hours at 40°C (according to DIN 50017) Testing of viscosity stability in case of shear loading For testing the viscosity stability in the case of shear loads, the basecoat lacquers described in E and F Clear lacquer extract (clear lacquer extract = pigment-free base lacquer) is foliar It was strongly stirred for 1 hour using a stirrer, and then sheared for 0 to 50 seconds in a viscometer. Sheared and measured at gradient. Transparent lacquer drawing of the undercoat love car described in E. The output showed a viscosity reduction of about 40%. Unlike this, the undercoat lacquer described in F. The clear lacquer extract of - showed only a lesser 10% viscosity reduction. the above A slight viscosity reduction has a negative influence on the application and settling behavior. not present.

H Preparation of pigment paste for water-based Uni base lacquer 10 parts by weight thickener (laminated structure) Sodium-magnesium-silicate with structure (3% in water) is charged to this 4.5 parts by weight of trimethylethanolamine solution (3% in water) with stirring, 2 parts by weight of polypropylene glycol (molecular weight 900), polyester described in D 4670 parts by weight of lubricant and 2335 parts by weight of deionized water are added. Next, The lower pigment is added separately and stirred into an Irgaz funnel. in Rot) DPP BO2, 65 parts by weight, Chromophthalrot (Crom ophtalrot) A 2 B 4, 38 parts by weight, Novo Palm Orange (Novoperm Orange) H2705, 29 parts by weight and Shikoton Yellow (5icotan GeLbe) 2 1912 1.13 parts by weight.

Finally, the mixture was homogenized in a routine laboratory dissolver for 20 minutes. Ru. This was subsequently carried out in a conventional laboratory ball mill with a Hegmann (t legmann) (ISo 152).

The pH value of the pigment paste is between 8 and 85, and usually the pH value is dimethyl ethanol. The above values are adjusted with a solution of amine (10% in water).

Ciba Geigy products Hoechst products of Manufacture of water-based Uni undercoat rough car, a product of Peeny Nissf Co., Ltd. (BASF). Two unique base lacquers are produced using pigment pastes and the listed ingredients. In this case Unibase Lacquer 2 is considered as a comparative example. two base coats For lacquers, the weight ratio of pigment to solid resin and male formaldehyde The weight ratio of OH-containing solid resin to hydro resin is equal.

Uni Undercoat Rough Car 2 Pigment Paste 41.33 33 ．． According to 57A 2 By polyacrylate resin 25.77-B Polyacrylate resin -2090 Luwipa! LR 87895,884,77 Resimene 4518 0.92 0.75 Deionized water 26.10 40.01 The above ingredients are mixed sequentially with stirring. Numbers are in parts by weight.

The base lacquer thus obtained is adjusted to a viscosity of 28s (DIN 4) . Unibase lacquer 1 has a solids content of 34% by weight (1 hour) at the stated viscosities. 130° C.) and Unibase Lacquer 2 has a solids content of 283% by weight (1 time, 130°C).

J. Application and testing of Uni base lacquer ■ Water-based Uni manufactured as described in ■ - After storage for 48 hours, the base lacquer can be mixed with commercially available electrocoated coatings and Laminated with commercially available fillers and applied onto phosphated iron plates. 60% relative At humidity and temperature of 23 ° C, air spraying using a pressure vessel is applied, after the first application 2 minutes intermediate evacuation, 1 minute evacuation after second application and in a circulating air oven at 80 °C. Two applications with 10 minutes drying. After this, commercially available transparent lacquers are Applied over a rylate/maleic formaldehyde resin substrate and cooled for a short time. and baked at 130℃ for 30 minutes. Testing of the two-layer coating thus obtained yielded the following results: 2 layers using Uni base coat lacquer 1 and 2 layers coating film using Uni base coat lacquer 2 Paint film (Steinschlag) Fundamentals test 00 Gloss 20° 87 87 Boiling limit 45μm 28μm Stretching limit 45μm 24μm VDA: German Automobile Industry Association: Impact medium square blasting material 1000g : Particle size: 4-5mm; Pressure: 1.5 bar, VDA certified sun blasting! Record Application according to the method described: In the case of boiling spraying of the above-mentioned basecoat lacquer, the basecoat Producing the thickness of the lacquer film Application according to the method described: boiling of the base lacquer on vertically erected perforated plates In the case of spraying, the thickness of the base lacquer film is increased and the thickness of the base lacquer layer is Stretching occurs during subsequent predrying in a vertical position.

Summary book Process for producing multicoat lacquer coatings and aqueous basecoat lacquers suitable for this process The present invention deals with the treatment of a monomer having a carboxyl group and a carboxyne group in an organic solvent. A polyacrylate resin is produced by polymerizing monomers having the following properties sequentially or alternately in partial amounts. to at least partially neutralize the polyacrylate resin and submerge it in water. A base containing water-dilutable polyacrylate resin obtained by dispersing This invention relates to an undercoat lacquer for producing clear coat type coatings.

Procedural manuscript (self-motivated) 1.Display of the incident PCT/EP　91100448 2. Name of the invention Method for producing multilayer lacquer coatings and aqueous basecoat lacquers suitable for this method 3. Person who makes corrections Relationship to the incident: Patent applicant Name: Beaninisev Ranoke Lant Farben Akchengesersi shaft 4. Agent Address: 3-3-1 Marunouchi, Chiyoda-ku, Tokyo 100-:, l’-5,: 5. Number of claims increased by amendment 06. Subject of amendment Description and claims 7. Contents of amendment (1) r(bl)J on page 6, line 3 of the specification is “not having a carboxyl group (bl) ) Correct as J.

(2) Amend the scope of claims as shown in the attached sheet.

The scope of the claims 1. (1) As the undercoat lacquer, a water-based undercoat lacquer containing pigment is applied to the surface of the support. applied on the surface, (2) A thin polymer film is formed from the lacquer applied in step (1); (3) A transparent top lacquer is applied on the base layer thus obtained, and then (4) the base layer is baked together with the top lacquer; A method for producing multilayer coatings, protective coatings and/or decorative coatings, in which the Undercoating and coating (I) (al) has few (both have one carboxyl group) per molecule, (bl), ( b2), an ethylenically unsaturated monomer copolymerizable with (b3) and (a2), or A mixture consisting of such monomers contains 2.5 to 15 weight U and (a2) does not have a carboxyl group, (bl), (b2), (b3) and (a ethylenically unsaturated monomer copolymerizable with l) or a mixture consisting of such monomers; 0 to 60% by weight of the compound and (bl) (b2), (b3), (al) and (a (meth)acrylic acid ester which can be copolymerized with 2) and has essentially no carboxyl group. ster or a mixture consisting of such (meth)acrylic esters 40-90 weight% and (b2) Can be copolymerized with (bl), (b3), (al) and (a2), 1 molecule having at least one hydroxyl group and essentially carboxyl groups Ethylenically unsaturated monomers or mixtures consisting of such monomers 45% by weight and (b3) copolymerizable with (bl), (b2), (al) and (a2), essentially Ethylene-based, different from (bl) and (b2), which does not have a carboxyl group in 0-40% by weight of unsaturated monomers or mixtures of such monomers component (b) consisting sequentially or alternately in portions of an organic solvent or solvent mixture; (II) polymerization in the presence of at least one polymerization initiator; After curing, the polyacrylate resin obtained is at least partially neutralized and in this case (al), (a2), (bl), (b2) and (b3) The sum of the weights of is always 100% by weight, and (bl), (b2), (b3 ), (al) and (a2) are obtained by selecting them in terms of type and amount. A multilayer coating characterized by containing a water-dilutable polyacrylate resin Process for producing membranes, protective coatings and/or decorative coatings.

2. In aqueous lacquers containing pigments, at least 1 per molecule of (al) (bl), (b2), (b3) and (a2), each having a carboxyl group of Copolymerizable ethylenically unsaturated monomer or mixture consisting of such monomers 2 ．． 5-15 weight 4 voices (a2) does not have a carboxyl group, (bl), (b2), (b3) and (a ethylenically unsaturated monomer copolymerizable with l) or a mixture consisting of such monomers; μ and (b1) (b, 2), (b3), (al) and the compound 0 to 60 weight (meth)acrylic acid which is copolymerizable with and (a2) and essentially has no carboxyl group Lyric esters or mixtures of such (meth)acrylic esters 4 0-90 weight - top and (b2) Can be copolymerized with (bl), (b3), (al) and (a2), 1 molecule having at least one hydroxyl group and essentially carboxyl groups Ethylenically unsaturated monomers or mixtures consisting of such monomers 45% by weight and (b3) copolymerizable with (bl), (b2), (al) and (a2), essentially Ethylene-based, different from (bl) and (b2), which does not have a carboxyl group in 0-40% by weight of unsaturated monomers or mixtures of such monomers component (b) consisting sequentially or alternately in portions of an organic solvent or solvent mixture; (II) polymerization in the presence of at least one polymerization initiator; After curing, the polyacrylate resin obtained is at least partially neutralized and in this case (al), (a2), (bl), (b2) and (b3) The total weight of bones is always 100% by weight, and (bl), (b2), (b3 ), (al) and (a2) are polyacrylate resins in terms of type and I. Water dilutable polyacrylic obtained by selecting 0 to 200 hydroxy Pigment-containing water-based lacquer, characterized in that it contains a rate resin.

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Claims (1)

[Claims] 1. (1) As an undercoat lacquer, a water-based undercoat lacquer containing pigment is applied to the surface of the support. (2) a thin polymer film is formed from the lacquer applied in step (1); Re, (3) A transparent top lacquer is applied on the base layer thus obtained, and then (4) the base layer is baked together with the top lacquer; A method for producing multilayer coatings, protective coatings and/or decorative coatings, in which the Undercoat lacquer (I) (a1) having at least one carboxyl group per molecule, (b1), ( b2), an ethylenically unsaturated monomer copolymerizable with (b3) and (a2), or The mixture of such monomers contains 2.5 to 15% by weight, preferably 3 to 7% by weight. Beauty (a2) does not have a carboxyl group, (b1), (b2), (b3) and (a Ethylenically unsaturated monomer copolymerizable with 1) or a mixture of such monomers 0 to 60% by weight, preferably 0 to 28% by weight of the compound and (b1) copolymerizable with (b2), (b3), (a1) and (a2), essentially (meth)acrylic acid esters without carboxyl groups or such (meth)acrylic esters g) 40 to 90% by weight, preferably 40 to 80% by weight of a mixture consisting of acrylic esters; Amount% and (b2) Can be copolymerized with (b1), (b3), (a1) and (a2), 1 molecule having at least one hydroxyl group and essentially carboxyl groups Ethylenically unsaturated monomers or mixtures consisting of such monomers 45% by weight, preferably 4-34% by weight and (b3) copolymerizable with (b1), (b2), (a1) and (a2) and essentially Ethylene-based, different from (b1) and (b2), which does not have a carboxyl group in 0 to 40% by weight of unsaturated monomers or mixtures of such monomers, preferably 1 0-30% by weight component (b) consisting sequentially or alternately in portions of an organic solvent or solvent mixture; and polymerize in the presence of at least one polymerization initiator, (II) After termination of the polymerization, the obtained polyacrylate resin is at least partially neutralized and dispersed in water, in this case (a1), (a2), (b1), (b2 ) and (b3) are always 100% by weight, and (b1), (b2), (b3), (a1) and (a2) are polyamines in terms of type and amount. The acrylate resin has a hydroxyl number of 0 to 200, especially 20 to 120, 20 to 10 0, especially an acid value of 25 to 50 and -40°C to +60°C, especially -20°C to +40°C The water dilute obtained by selecting the glass transition temperature (Tc) of Multi-layer coating film, protective coating, characterized by containing polyacrylate resin that can be used Method for producing membranes and/or decorative coatings. 2. In a pigment-containing aqueous lacquer, (I) (a1) having at least one carboxyl group per molecule, (b1), ( b2), an ethylenically unsaturated monomer copolymerizable with (b3) and (a2), or The mixture of such monomers contains 2.5 to 15% by weight, preferably 3 to 7% by weight. Beauty (a2) does not have a carboxyl group, (b1), (b2), (b3) and (a Ethylenically unsaturated monomer copolymerizable with 1) or a mixture consisting of such monomers 0 to 60% by weight, preferably 0 to 28% by weight of the compound and (b1) copolymerizable with (b2), (b3), (a1) and (a2), essentially (meth)acrylic acid esters without carboxyl groups or such (meth)acrylic esters g) 40 to 90% by weight, preferably 40 to 80% by weight of a mixture consisting of acrylic esters; Amount% and (b2) Can be copolymerized with (b1), (b3), (a1) and (a2), 1 molecule having at least one hydroxyl group and essentially carboxyl groups Ethylenically unsaturated monomers or mixtures consisting of such monomers 45% by weight, preferably 4-34% by weight and (b3) copolymerizable with (b1), (b2), (a1) and (a2) and essentially Ethylene-based, different from (b1) and (b2), which does not have a carboxyl group in 0 to 40% by weight of unsaturated monomers or mixtures of such monomers, preferably 1 0-30% by weight component (b) consisting sequentially or alternately in portions of an organic solvent or solvent mixture; and polymerize in the presence of at least one polymerization initiator, (II) After termination of the polymerization, the obtained polyacrylate resin is at least partially neutralized and dispersed in water, in this case (a1), (a2), (b1), (b2 ) and (b3) are always 100% by weight, and (b1), (b2), (b3), (a1) and (a2) are polyamines in terms of type and amount. The acrylate resin has a hydroxyl number of 0 to 200, especially 20 to 120, 20 to 10 0, especially an acid value of 25 to 50 and -40°C to +60°C, especially -20°C to +40°C The water dilute obtained by selecting the glass transition temperature (Tc) of Pigment-containing water, characterized in that it contains a polyacrylate resin that can be mixed with pigments. Sex lacquer. 3. The claimed base lacquer contains metallic pigments or mixtures consisting of metallic pigments. A method or lacquer according to scope 1 or 2. 4. Primer lacquer or lacquer with water-dilutable polyacrylate resin Water-dilutable polyurethane resin and/or water-dilutable polyester Claim 1 containing a resin and/or a water-dilutable aminoplast resin A method or a lacquer according to any one of claims 3 to 3. 5. The base lacquer or lacquer consists of non-metallic pigments or non-metallic pigments. 10 to 95% by weight of the mixture and (A) water-dilutable polyacrylate resin, advantageously 25-70% by weight, (B) 5 to 50% by weight of aminoplast resin, preferably 10 to 40% by weight; (C) Water-dilutable polyester resin 0-85% by weight, preferably 20-60% by weight and (D) Water-dilutable polyurethane resin 0-85% by weight, preferably 0-40% by weight In this case, the sum of the weight proportions of components (A) to (D) is always The method according to any one of claims 1 to 4, or 100% by weight of or lacquer. 6. The base lacquer or lacquer contains metallic pigments and (A) 10 to 95% by weight of water-dilutable polyacrylate resin, preferably 25 to 70% by weight; weight%, (B) 5 to 50% by weight of aminoplast resin, preferably 10 to 40% by weight; (C) Water-dilutable polyester resin 0-85% by weight, preferably 20-60% by weight and (D) Water-dilutable polyurethane resin 0-85% by weight, preferably 0-40% by weight In this case, the sum of the weight proportions of components (A) to (D) is always The method according to any one of claims 1 to 5, or 100% by weight of or lacquer. 7. Water-dilutable polyester resin is made from (α) polyol or polyol mixture, (β) polycarboxylic acid or polycarboxylic acid anhydride or polycarbonate A mixture consisting of carboxylic acid and/or polycarboxylic acid anhydride 00, preferably a number average molecular weight of 800 to 2500, 20 to 70, preferably 25 to 55 and a hydroxyl number of from 30 to 200, preferably from 45 to 100. converting the resulting polyester resin into an ester resin, and at least partially converting the resulting polyester resin into an ester resin; obtained by neutralizing, in this case, - components (α) and (β) are between 1.15 and 2.00:1, preferably between 1.2 and 1.5; : component (α) is used in a molar ratio of 30 to 100% by weight as secondary or secondary Aliphatic with at least one α-C atom that is a member of a tertiary or carbon-containing ring system Component (β) is composed of diol, and 50 to 100% by weight of the component (β) is an aromatic polycarbonate. phosphoric acid and/or alicyclic polycarboxylic acid, and 15 to 40% by weight is consisting of carboxylic acids and/or tetracarboxylic acids, in which case tricarboxylic acids Acids and/or tetracarboxylic acids are those in which the acid has at least two carboxyl groups. from claim 4, wherein the polyester resin is used to be introduced into the polyester resin molecule by 6. The method or lacquer according to any one of claims 6 to 6. 8. Component (β) is 50 to 80 mol% aromatic polycarboxylic acid and/or fat. cyclic polycarboxylic acid, and 20 to 50 mol% of one or more polycarboxylic acids. Consisting of molecular weight fatty acids, in this case high molecular weight fatty acids are cycloaliphatic polycarboxylic acids. The method or lacquer according to claim 7, which is not considered. 9. Multi-layer coatings of the base coat/clear coat type, protective coatings and/or decorative coatings According to any one of claims 2 to 8 as a base lacquer for the manufacture of Use of water-based lacquers as described.